The process products are used, inter alia, as intermediates in the production of fuel additives (U.S. Pat. No. 3,275,554 A; DE 21 25 039 A and DE 36 11 230 A), surfactants, drugs and crop protection agents, hardeners for epoxy resins, catalysts for polyurethanes, intermediates for preparing quaternary ammonium compounds, plasticizers, corrosion inhibitors, synthetic resins, ion exchangers, textile assistants, dyes, vulcanization accelerators and/or emulsifiers.
EP 257 443 A (BASF AG) relates to a process for the preparation of trialkylamines (e.g. dimethylethylamine) by reaction of ammonium with alcohols in the presence of alkali metal hydroxide in the liquid phase over a catalyst comprising essentially only copper.
EP 227 904 A (BASF AG) teaches the preparation of dimethylethylamine or N,N-dimethylcyclohexylamine in the liquid phase by reaction of dimethylamine with cyclohexanol in the presence of alkali metal hydroxide and a catalyst which comprises essentially only copper as active metal or is a pure copper catalyst.
U.S. Pat. No. 4,910,304 A (BASF AG) discloses the preparation of N-methylpiperidine and N-methylmorpholine by reaction of pentanediol or diethylene glycol (DEG) with methylamine and 45% strength aqueous KOH solution over an all-active Cu/Al catalyst at 245° C. and 250 bar.
EP 137 478 A (BASF AG) relates to a process for preparing N-methylpiperidine or N-methylmorpholine by catalytic amination of pentanediol by means of methylamine in the gas phase at from 5 to 25 bar over a copper-comprising catalyst which has been obtained by heating a basic copper- and aluminum-comprising carbonate.
EP 235 651 A1 (BASF AG) teaches a process for preparing N-methylpiperazine from diethanolamine and methylamine over metal-comprising catalysts. The reaction is carried out in the liquid phase (downflow mode) (page 3, last paragraph). According to an example, a Cu/Al2O3 catalyst in pellet form, height=diameter=4 mm, is used.
EP 816 350 A (BASF AG) describes a process for preparing N-methylpiperidine and N-methylmorpholine by reaction of primary amine with a diol in the liquid or gas phase over a copper catalyst which has been obtained by impregnation of SiO2 spheres with basic copper carbonate.
U.S. Pat. No. 4,739,051 A (BASF AG) teaches the preparation of morpholine and piperidine by reaction of DEG or pentanediol with ammonia under hydrogenation conditions in the gas phase at atmospheric pressure and 200° C. over an all-active Cu/Ni/Al catalyst in yields of 97 or 95%.
EP 514 692 A2 (BASF AG) discloses a process for preparing amines from alkohols in the presence of catalysts comprising copper and nickel and zirconium oxide and/or aluminum oxide.
EP 1 020 455 A (BASF AG) relates to a process for preparing bis(2-morpholinoethyl)ether by reaction of diethylene glycol (DEG) with ammonia under superatmospheric pressure and at elevated temperature in the presence of hydrogen and a copper-comprising hydrogenation catalyst.
EP 1 106 600 A (BASF AG) teaches the use of ZrO2—Cu—Co—Ni catalysts in amination reactions. According to an example, 5×3 mm pellets are used as shaped catalyst bodies.
U.S. Pat. No. 4,806,690 A (Dow Chemical Comp.) relates to the amination of alcohols, aldehydes and ketones in the presence of a Co—Cu—Fe and Zn and/or Zr catalysts. In an example, 8-16 mesh catalyst particles are used.
DE 19 85 9776 A (BASF AG) relates to the preparation of amines by reaction of alcohols or aldehydes or ketones with amines over a catalyst which comprises copper and TiO2 and to which metallic copper has been added prior to shaping of the catalyst material. According to an example, the catalyst is used as pellets having a diameter of 3 mm.
EP 440 829 A1 (U.S. Pat. No. 4,910,304) (BASF AG) describes the amination of diols over copper catalysts. The reaction is carried out in the liquid phase (downflow mode) (page 3, last paragraph). Suitable catalysts are the catalysts disclosed in DE 24 45 303 A (BASF AG) which can be obtained by heating a basic copper- and aluminum-comprising carbonate of the general composition CumAl6(CO3)0.5mO3(OH)m+12, where m is any, not necessarily integral, number from 2 to 6, for example the copper-comprising precipitated catalyst disclosed in loc. cit., example 1, which is prepared by treatment of a solution of copper nitrate and aluminum nitrate with sodium bicarbonate and subsequent washing, drying and heat treatment of the precipitate.
In the examples of EP 440 829 A, the catalyst is used as cylindrical shaped bodies having a length of 3 mm and a diameter of 3 mm.
WO 07/036,496 A1 (BASF AG) describes the reaction of diethylene glycol with ammonia in the presence of Cu—Ni—Co catalysts. The shaped catalyst body has, in the case of a pellet shape, a height of <3 mm.
WO 07/036,498 A1 (BASF AG) relates to the reaction of monoethanolamine with ammonia in the presence of Cu—Ni—Co catalysts. The shaped catalyst body has, in the case of a pellet shape, a height of <3 mm.
WO 07/093,514 A1 and WO 07/093,552 A1 (both BASF AG) teach the reaction of monoethylene glycol with ammonia in the presence of Ru—Co catalysts. The shaped catalyst body has, in the case of a pellet shape, a height of <3 mm.
WO 05/110969 A1 (BASF AG) describes a process for the continuous preparation of an amine by reaction of a primary or secondary alcohol, aldehyde and/or ketone with hydrogen and a nitrogen compound selected from the group consisting of ammonia, primary and secondary amines at a temperature in the range from 60 to 300° C. in the presence of a copper-comprising catalyst, with the catalytically active composition of the catalyst before reduction with hydrogen comprising from 20 to 85% by weight of aluminum oxide (Al2O3), zirconium dioxide (ZrO2), titanium dioxide (TiO2) and/or silicon dioxide (SiO2) and the reaction being carried out isothermally in the gas phase in a tube reactor.